Synthetic polymers comprising additive blends with enhanced effect

ABSTRACT

The dispersion of additives selected from the group consisting of stabilizers, antistatic agents, nucleating agents, biocides and/or flame retardants in synthetic polymers is improved by the addition of at least one polymeric dispersing or solvating agent having amphiphilic properties. Synthetic polymers stabilized in this manner are distinguished by having excellent stability against oxidative, thermal or light-induced degradation.

The present invention relates to compositions comprising a syntheticpolymer subject to oxidative, thermal or light-induced degradation, inparticular a thermoplastic polymer, and as additives at least oneadditive selected from the stabiliser, antistatic agent, nucleatingagent, biocide and/or flame retardant group, and at least one polymericdispersing or solvating agent having amphiphilic properties, to the useof these additives in synthetic polymers, in particular thermoplasticpolymers, as well as to a process for stabilising these syntheticpolymers, with the proviso that at least one additive contains acompound from the stabiliser group.

This invention also relates to the use of the polymeric dispersing orsolvating agents having amphiphilic properties for the improveddispersion of additives selected from the stabiliser, antistatic agent,nucleating agent and/or biocide group in synthetic polymers, and to aprocess for the improved dispersion of additives selected from thestabiliser, antistatic agent, nucleating agent and/or biocide group insynthetic polymers.

The effect of synthetic additives depends, for example, on the chemicalstructure of the additives, on the composition of additive blends, onthe dispersion of the additives in the plastic material, on thesolubility of the additives in the respective polymer and on thecompatibility of the additives with the polymeric matrix. An enhancedcompatibility of additives with polymeric substrates, and thus anenhanced effect, can be achieved, for example, through the preparationof preblends. So-called masterbatches or concentrates, which are apreblend of a polymer with additives in high concentrations, are alsooften used, the subsequent use of this masterbatch making it possiblefor the additive to be dispersed in the polymer matrix more easily andbetter than when it is added directly. Although these techniques arevery well known, methods are still sought by which the performance ofadditives may be further improved, i.e. for making full use of them.

Accordingly, this invention has for its object to provide compositionswhich enhance the effect of existing additives in synthetic polymers, inparticular by improved dispersion.

U.S. Pat. No. 5,387,467 discloses the use of organopolysiloxanes withester groups and long-chain alkyl groups, said groups being bound viacarbon atoms to silicium atoms, for modifying the surface of fineparticles, such as pigments and fillers, or of glass fibres.

It has now been found that the effect of additives selected from thestabiliser, antistatic agent, nucleating agent, biocide and/or flameretardant group in synthetic polymers is enhanced by the addition of atleast one polymeric dispersing or solvating agent having amphiphilicproperties. Synthetic polymers thus enhanced are distinguished by havingexcellent stability against oxidative, thermal or light-induceddegradation.

This invention therefore relates to compositions, which comprise

a) a synthetic polymer subject to oxidative, thermal or light-induceddegradation,

b) at least one additive selected from the stabiliser, antistatic agent,nucleating agent, biocide and/or flame retardant group, and

c) at least one polymeric dispersing or solvating agent havingamphiphilic properties.

Examples of antistatic agents are described in R. Gächter and H. Müller,Hanser Verlag, 3^(rd) edition, 1990, pages 749-775. Particularlyinteresting antistatic agents are those selected from the groupconsisting of the ethoxylated alkylamines, fatty acid esters, alkylsulfonates and polymeric systems based on polyamide copolymers, such asIrgastat®P22, of Ciba Spezialitätenchemie.

Examples of biocides are described in R. Gächter and H. Müller, HanserVerlag, 3^(rd) edition, 1990, pages 791-809. Particularly interestingbiocides are those selected from the group consisting of the10,10′-oxy-bis-phenoxarsines, N-(trihalogenomethlythio)phthalimides,di-phenyl-antimonium-2-ethylhexanoate, copper-bis(8-hydroxyquinoline),tributyltin oxide and the derivatives thereof; halogenated phenols, suchas Irgaguard® (Trichlosan CAS number 3380-34-5, Ciba SpezialitätenchemieAG); methylthio-s-triazines, such as2-methylthio-4-cyclopropylamino-6-(α, β-dimethylpropylamino)-s-triazine,2-methylthio-4-cyclopropylamino-6-tert-butylamino-s-triazine and2-methylthio-4-ethylamino-6-(α, β-dimethylpropylamino)-s-triazine.

Preferred compositions are those, wherein component (b) is a stabiliserand/or nucleating agent.

Examples of stabilisers are the following:

1. Antioxidants

1.1. Alkylated monophenols, for example2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4,6-dimethylphenol,2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4-n-butylphenol,2,6-di-tert-butyl-4-isobutylphenol, 2,6-dicyclopentyl-4-methylphenol,2-(α-methylcyclohexyl)-4,6-dimethylphenol,2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol,2,6-di-tert-butyl-4-methoxymethylphenol, nonylphenols which are linearor branched in the side chains, for example,2,6-di-nonyl-4-methylphenol, 2,4dimethyl-6-(1′-methylundec-1′-yl)phenol,2,4-dimethyl-6-(1′-methylheptadec-1′-yl)phenol,2,4-dimethyl-6-(1′-methyltridec-1′-yl)phenol and mixtures thereof.

1.2. Alkylthiomethylphenols, for example2,4-dioctylthiomethyl-6-tert-butylphenol,2,4-dioctylthiomethyl-6-methylphenol,2,4-dioctylthiomethyl-6-ethylphenol,2,6-di-dodecylthiomethyl-4-nonylphenol.

1.3. Hydroquinones and alkylated hydroquinones, for example2,6-di-tert-butyl-4-methoxyphenol, 2,5-di-tert-butylhydroquinone,2,5-di-tert-amylhydroquinone, 2,6-diphenyl-4-octadecyloxyphenol,2,6-di-tert-butylhydroquinone, 2,5-di-tert-butyl-4-hydroxyanisole,3,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyphenylstearate, bis-(3,5-di-tert-butyl-4-hydroxyphenyl)adipate.

1.4. Tocopherols, for example α-tocopherol, β-tocopherol, γ-tocopherol,δ-tocopherol and mixtures thereof (Vitamin E).

1.5. Hydroxylated thiodiphenyl ethers, for example2,2′-thiobis(6-tert-butyl-4-methylphenol), 2,2′-thiobis(4-octylphenol),4,4′-thiobis(6-tert-butyl-3-methylphenol),4,4′-thiobis(6-tert-butyl-2-methylphenol),4,4′-thiobis-(3,6-di-sec-amylphenol),4,4′-bis(2,6-dimethyl-4-hydroxyphenyl)disulfide.

1.6. Alkylidenebisphenols, for example2,2′-methylenebis(6-tert-butyl-4-methylphenol),2,2′-methylenebis(6-tert-butyl-4-ethylphenol),2,2′-methylenebis[4-methyl-6-(α-methylcyclohexyl)phenol],2,2′-methylenebis(4-methyl-6-cyclohexylphenol),2,2′-methylenebis(6-nonyl-4-methylphenol),2,2′-methylenebis(4,6-di-tert-butylphenol),2,2′-ethylidenebis(4,6-di-tert-butylphenol),2,2′-ethylidenebis(6-tert-butyl-4-isobutylphenol),2,2′-methylenebis[6-(α-methylbenzyl)-4-nonylphenol],2,2′-methylenebis[6-(α,α-dimethylbenzyl)-4-nonylphenol],4,4′-methylenebis(2,6-di-tert-butylphenol),4,4′-methylenebis(6-tert-butyl-2-methylphenol),1,1-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)butane,2,6-bis(3-tert-butyl-5-methyl-2-hydroxybenzyl)-4-methylphenol,1,1,3-tris(5-tert-butyl-4-hydroxy-2-methylphenyl)butane,1,1-bis(5-tert-butyl-4-hydroxy-2-methyl-phenyl)-3-n-dodecylmercaptobutane,ethylene glycol bis[3,3-bis(3′-tert-butyl-4′-hydroxyphenyl)butyrate],bis(3-tert-butyl-4-hydroxy-5-methyl-phenyl)dicyclopentadiene,bis[2-(3′-tert-butyl-2′-hydroxy-5′-methylbenzyl)-6-tert-butyl-4-methylphenyl]terephthalate,1,1-bis-(3,5-dimethyl-2-hydroxyphenyl)butane,2,2-bis-(3,5-di-tert-butyl-4-hydroxyphenyl)propane,2,2-bis-(5-tert-butyl-4-hydroxy2-methylphenyl)-4-n-dodecylmercaptobutane,1,1,5,5-tetra-(5-tert-butyl-4-hydroxy-2-methylphenyl)pentane.

1.7. O-, N- and S-benzyl compounds, for example3,5,3′,5′-tetra-tert-butyl-4,4′-dihydroxydibenzyl ether,octadecyl-4-hydroxy-3,5-dimethylbenzylmercaptoacetate,tridecyl-4-hydroxy-3,5-di-tert-butylbenzylmercaptoacetate,tris(3,5-di-tert-butyl-4-hydroxybenzyl)amine,bis(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)dithioterephthalate,bis(3,5-di-tert-butyl-4-hydroxybenzyl)sulfide,isooctyl-3,5-di-tertbutyl-4-hydroxybenzylmercaptoacetate.

1.8. Hydroxybenzylated malonates, for exampledioctadecyl-2,2-bis-(3,5-di-tert-butyl-2-hydroxybenzyl)-malonate,di-octadecyl-2-(3-tert-butyl-4-hydroxy-5-methylbenzyl)-malonate,didodecylmercaptoethyl-2,2-bis-(3,5-di-tert-butyl-4-hydroxybenzyl)malonate,bis[4-(1,1,3,3-tetramethylbutyl)phenyl]-2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)malonate.

1.9. Aromatic hydroxybenzyl compounds, for example1,3,5-tris-(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene,1,4-bis(3,5-di-tert-butyl-4-hydroxybenzyl)-2,3,5,6-tetramethylbenzene,2,4,6-tris(3,5-di-tert-butyl4-hydroxybenzyl)phenol.

1.10. Triazine Compounds, for example2,4-bis(octylmercapto)-6-(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-triazine,2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-triazine,2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,3,5-triazine,2,4,6-tris-(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,2,3-triazine,1,3,5-tris-(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate,1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurate,2,4,6-tris-(3,5-di-tert-butyl-4-hydroxyphenylethyl)-1,3,5-triazine,1,3,5-tris(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-hexahydro-1,3,5-triazine,1,3,5-tris(3,5-dicyclohexyl-4-hydroxybenzyl)isocyanurate.

1.11. Benzylphosphonates, for exampledimethyl-2,5-di-tert-butyl-4-hydroxybenzylphosphonate,diethyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate,dioctadecyl3,5-di-tert-butyl-4-hydroxybenzylphosphonate,dioctadecyl-5-tert-butyl-4-hydroxy-3-methylbenzylphosphonate, thecalcium salt of the monoethyl ester of3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid.

1.12. Acylaminorhenols, for example 4-hydroxylauranilide,4-hydroxystearanilide, octyl.N-(3,5-di-tert-butyl-4-hydroxyphenyl)carbamate.

1.13. Esters of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid withmono- or polyhydric alcohols, e.g. with methanol, ethanol, n-octanol,i-octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol,1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethyleneglycol, triethylene glycol, pentaerythritol,tris(hydroxyethyl)isocyanurate, N,N′-bis(hydroxyethyl)oxamide3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol,trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.

1.14. Esters of β-(5-tert-butyl-4-hydroxy-3-methylphenyl)propionic acidwith mono- or polyhydric alcohols, e.g. with methanol, ethanol,n-octanol, i-octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol,ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethyleneglycol, diethylene glycol, triethylene glycol, pentaerythritol,tris(hydroxyethyl)isocyanurate, N,N′-bis-(hydroxyethyl)oxamide,3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol,trimethylolpropane,4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.

1.15. Esters of β-(3.5-dicyclohexyl-4-hvdroxyphenyl)prorionic acid withmono- or polyhydric alcohols, e.g. with methanol, ethanol, octanol,octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol,1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethyleneglycol, triethylene glycol, pentaerythritol,tris(hydroxyethyl)isocyanurate, N,N′-bis(hydroxyethyl)oxamide,3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol,trimethylolpropane,4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.

1.16. Esters of 3.5-di-tert-butyl-4-hydroxyphenyl acetic acid with mono-or polyhydric alcohols, e.g. with methanol, ethanol, octanol,octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol,1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethyleneglycol, triethylene glycol, pentaerythritol,tris(hydroxyethyl)isocyanurate, N,N′-bis(hydroxyethyl)oxamide,3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol,trimethylolpropane,4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.

1.17. Amides of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid e.g.N,N′-bis(3,5-di-tertbutyl-4-hydroxyphenylpropionyl)hexamethylenediamide,N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)trimethylenediamide,N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hydrazide,N,N′-bis[2-(3-[3,5-di-tert-butyl-4-hydroxyphenyl]propionyloxy)ethyl]oxamide(Naugard®XL-1 supplied by Uniroyal).

1.18. Ascorbic acid (vitamin C)

1.19. Aminic antioxidants, for exampleN,N′-di-isopropyl-p-phenylenediamine,N,N′-di-sec-butyl-p-phenylenediamine,N,N′-bis(1,4-dimethylpentyl)-p-phenylenediamine,N,N′-bis(1-ethyl-3-methylpehtyl)-p-phenylenediamine,N,N′-bis(1-methylheptyl)-p-phenylenediamine,N,N′-dicyclohexyl-p-phenylenediamine, N,N′-diphenyl-p-phenylenediamine,N,N′-bis(2-naphthyl)-p-phenylenediamine,N-isopropyl-N′-phenyl-p-phenylenediamine,N-(1,3-dimethylbutyl)-N′-phenyl-p-phenylenediamine,N-(1-methylheptyl)-N′-phenyl-p-phenylenediamine,N-cyclohexyl-N′-phenyl-p-phenlenediamine,4-(p-toluenesulfamoyl)diphenylamine,N,N′-dimethyl-N,N′-di-sec-butyl-p-phenylenediamine, diphenylamine,N-allyldiphenylamine, 4-isopropoxydiphenylamine,N-phenyl-1-naphthylamine, N-(4-tert-octylphenyl)-1-naphthylamine,N-phenyl-2-naphthylamine, octylated diphenylamine, for examplep,p′-di-tert-octyldiphenylamine, 4-n-butylaminophenol,4-butyrylaminophenol, 4-nonanoylaminophenol, 4-dodecanoylaminophenol,4-octadecahoylaminophenol, bis(4-methoxyphenyl)amine,2,6-di-tert-butyl-4-dimethylaminomethylphenol,2,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylmethane,N,N,N′,N′-tetramethyl-4,4′-diaminodiphenylmethane,1,2-bis[(2-methylphenyl)amino]ethane, 1,2-bis(phenylamino)propane,(o-tolyl)biguanide, bis[4-(1′,3′-dimethylbutyl)phenyl]amine,tert-octylated N-phenyl-1-naphthylamine, a mixture of mono- anddialkylated tert-butyl/tert-octyldiphenylamine, a mixture of mono- anddialkylated nonyldiphenylamines, a mixture of mono- and dialkylateddodecyldiphenylamines, a mixture of mono- and dialkylatedisopropyl/isohexyldiphenylamines, a mixture of mono- und dialkylatedtert-butyldiphenylamines, 2,3-dihydro-3,3-dimethyl-4H-1,4-benzothiazine,phenothiazine, a mixture of mono- und dialkylatedtert-butyl/tert-octylphenothiazines, a mixture of mono- und dialkylatedtert-octyl-phenothiazines, N-allylphenothiazin,N,N,N′,N′-tetraphenyl-1,4-diaminobut-2-ene,N,N-bis(2,2,6,6-tetramethylpiperid-4yl-hexamethylenediamine,bis(2,2,6,6-tetramethylpiperid-4-yl)sebacate,2,2,6,6-tetramethylpiperidin-4-one, 2,2,6,6-tetramethylpiperidin-4-ol.

2. UV Absorbers and light Stabilisers

2.1. 2-(2′-Hydroxyphenyl)benzotriazoles, for example2-(2′-hydroxy-5′-methylphenyl)-benzotriazole,2-(3′,5′-di-tert-butyl-2′-hydroxyphenyl)benzotriazole,2-(5′-tert-butyl-2′-hydroxyphenyl)benzotriazole,2-(2′-hydroxy-5′-(1,1,3,3-tetramethylbutyl)phenyl)benzotriazole,2-(3′,5′-di-tert-butyl-2′-hydroxyphenyl)-5-chloro-benzotriazole,2-(3′-tert-butyl-2′-hydroxy-5′-methylphenyl)-5-chloro-benzotriazole,2-(3′-sec-butyl-5′-tert-butyl-2′-hydroxyphenyl)benzotriazole,2-(2′-hydroxy-4′-octyloxyphenyl)benzotriazole,2-(3′,5′-di-tert-amyl-2′-hydroxyphenyl)benzotriazole,2-(3′,5′-bis-(α,α-dimethylbenzyl)-2′-hydroxyphenyl)benzotriazole,2-(3′-tert-butyl-2′-hydroxy-5′-(2-octyloxycarbonylethyl)phenyl)-5-chloro-benzotriazole,2-(3′-tert-butyl-5′-[2-(2-ethylhexyloxy)-carbonylethyl]-2′-hydroxyphenyl)-5-chloro-benzotriazole,2-(3′-tert-butyl-2′-hydroxy-5′-(2-methoxycarbonylethyl)phenyl)-5-chloro-benzotriazole,2-(3′-tert-butyl-2′-hydroxy-5′-(2-methoxycarbonylethyl)phenyl)benzotriazole,2-(3′-tert-butyl-2′-hydroxy-5′-(2-octyloxycarbonylethyl)phenyl)benzotriazole,2-(3′-tert-butyl-5′-[2-(2-ethylhexyloxy)carbonylethyl]-2′-hydroxyphenyl)benzotriazole,2-(3′-dodecyl-2′-hydroxy-5′-methylphenyl)benzotriazole,2-(3′-tert-butyl-2′-hydroxy-5′-(2-isooctyloxycarbonylethyl)phenylbenzotriazole,2,2′-methylene-bis[4-(1,1,3,3-tetramethylbutyl)-6-benzotriazole-2-ylphenol];the transesterification product of2-[3′-tert-butyl-5′-(2-methoxycarbonylethyl)-2′-hydroxyphenyl]-2H-benzotriazolewith polyethylene glycol 300; [R—CH₂CH₂—COO—CH₂CH₂—]₂ whereR=3′-tert-butyl-4′-hydroxy-5′-2H-benzotriazol-2-ylphenyl,2-[2?-hydroxy-3′-(α,α-dimethylbenzyl)-5′-(1,1,3,3-tetramethylbutyl)-phenyl]benzotriazole;2-[2′-hydroxy-3′-(1,1,3,3-tetramethylbutyl)-5′-(α,α-dimethylbenzyl)-phenyl]benzotriazole.

2.2. 2-Hydroxybenzophenones, for example the 4-hydroxy, 4-methoxy,4-octyloxy, 4-decyloxy, 4-dodecyloxy, 4-benzyloxy, 4,2′,4′-trihydroxyand 2′-hydroxy-4,4′-dimethoxy derivatives.

2.3. Esters of substituted and unsubstituted benzoic acids, as forexample 4-tertbutyl-phenyl salicylate, phenyl salicylate, octylphenylsalicylate, dibenzoyl resorcinol, bis(4-tert-butylbenzoyl)resorcinol,benzoyl resorcinol, 2,4-di-tert-butylphenyl3,5-di-tert-butyl-4-hydroxybenzoate, hexadecyl3,5-di-tert-butyl-4-hydroxybenzoate, octadecyl3,5-di-tert-butyl-4-hydroxybenzoate, 2-methyl-4,6-di-tert-butylphenyl3,5-di-tert-butyl-4-hydroxybenzoate.

2.4. Acrylates, for example ethyl α-cyano-β,β-diphenylacrylate, isooctylα-cyano-β,β-diphenylacrylate, methyl α-carbomethoxycinnamate, methylα-cyano-β-methyl-p-methoxy-cinnamate, butylα-cyano-β-methyl-p-methoxy-cinnamate, methylα-carbomethoxy-p-methoxycinnamate andN-(β-carbomethoxy-β-cyanovinyl)-2-methylindoline.

2.5. Nickel compounds, for example nickel complexes of2,2′-thio-bis-[4-(1,1,3,3-tetramethylbutyl)phenol], such as the 1:1 or1:2 complex, with or without additional iigands such as n-butylamine,triethanolamine or N-cyclohexyldiethanolamine, nickeldibutyldithiocarbamate, nickel salts of the monoalkyl esters, e.g. themethyl or ethyl ester, of 4-hydroxy-3,5-di-tert-butylbenzylphosphonicacid, nickel complexes of ketoximes, e.g. of 2-hydroxy-4-methylphenylundecylketoxime, nickel complexes of1-phenyl-4-lauroyl-5-hydroxypyrazole, with or without additionalligands.

2.6. Sterically hindered amines, for examplebis(2,2,6,6-tetramethyl-4-piperidyl)sebacate,bis(22,26,6-tetramethyl-4-piperidyl)succinate,bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate,bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl)sebacate,bis(1,2,2,6,6-pentarhethyl-4-piperidyl)n-butyl-3,5-di-tert-butyl-4-hydroxybenzylmalonate, the condensate of1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4hydroxypiperidine and succinicacid, linear or cyclic condensates ofN,N′-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and4-tert-octylamino-2,6dichloro-1,3,5-triazine,tris(2,2,6,6-tetramethyl-4-piperidyl)nitrilotriacetate,tetrakis(2,2,6,6-tetramethyl-4-piperidyl)-1,2,3,4-butane-tetracarboxylate,1,1′-(1,2-ethanediyl)-bis(3,3,5,5-tetramethylpiperazinone),4-benzoyl-2,2,6,6-tetramethylpiperidine,4-stearyloxy-2,2,6,6-tetramethylpiperidine,bis(1,2,2,6,6-pentamethylpiperidyl)-2-n-butyl-2-(2-hydroxy-3,5-di-tert-butylbenzoyl)malonate,3-n-octyl-7,7,9,9-tetramethyl-1,3,8-trizaaspiro[4.5]decan-2,4-dione,bis(1-octyloxy-2,2,6,6-tetramethylpiperidyl)sebacate,bis(1-octyloxy-2,2,6,6-tetramethylpiperidyl)succinate, linear or cycliccondensates ofN,N′-bis-(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and4-morpholino-2,6-dichloro-1,3,5-triazine, the condensate of2-chloro-4,6-bis(4-n-butylamino-2,2,6,6-tetramethylpiperidyl)-1,3,5-triazineand 1,2-bis(3-aminopropylamino)ethane, the condensate of2-chlor-4,6-di-(4-n-butylamino-1,2,2,6,6-pentamethylpiperidyl)-1,3,5-triazineand 1,2-bis-(3-aminopropylamino)ethane,8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decane-2,4-dione,3-dodecyl-1-(2,2,6,6-tetramethyl-4-piperidyl)pyrrolidin-2,5-dione,3-dodecyl-1-(1,2,2,6,6-pentamethyl-4-piperidyl)pyrrolidine-2,5-dione, amixture of 4-hexadecyloxy- and4-stearyloxy-2,2,6,6-tetramethylpiperidine, a condensation product ofN,N′-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and4-cyclohexylamino-2,6-dichloro-1,3,5-triazine, a condensation product of1,2-bis(3-aminopropylamino)ethane and 2,4,6-trichloro-1,3,5-triazine aswell as 4-butylamino-2,2,6,6-tetramethylpiperidine (CAS Reg. No.[136504-96-6]); N-(2,2,6,6-tetramethyl-4-piperidyl)-n-dodecylsuccinimid,N-(1,2,2,6,6-pentamethyl-4-piperidyl)-n-dodecylsuccinimid,2-undecyl-7,7,9,9-tetramethyl-1-oxa-3,8-diaza-4-oxo-spiro[4,5]decane, areaction product of7,7,9,9-tetramethyl-2-cycloundecyl-1-oxa-3,8-diaza-4-oxospiro[4,5]decane und epichlorohydrin,1,1-bis(1,2,2,6,6-pentamethyl-4-piperidyloxycarbonyl)-2-(4-methoxyphenyl)ethene,N,N′-bis-formyl-N,N′-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine,diester of 4-methoxy-methylene-malonic acid with1,2,2,6,6-pentamethyl-4-hydroxypiperidine,poly[methylpropyl-3-oxy-4-(2,2,6,6-tetramethyl-4-piperidyl)]siloxane,reaction product of maleic acid anhydride-α-olefin-copolymer with2,2,6,6-tetramethyl-4-aminopiperidine or1,2,2,6,6-pentamethyl-4-aminopiperidine.

2.7. Oxamides, for example 4,4′-dioctyloxyoxanilide,2,2′-diethoxyoxanilide, 2,2′-dioctyloxy-5,5′-di-tert-butoxanilide,2,2′-didodecyloxy-5,5′-di-tert-butoxanilide, 2-ethoxy-2′-ethyloxanilide,N,N′-bis(3-dimethylaminopropyl)oxamide,2-ethoxy-5-tert-butyl-2′-ethoxanilide and its mixture with2-ethoxy-2′-ethyl-5,4′-di-tert-butoxanilide, mixtures of o- andp-methoxy-disubstituted oxanilides and mixtures of o- andp-ethoxy-disubstituted oxanilides.

2.8. 2-(2-Hydroxyphenyl)-1,3,5-triazines, for example2,4,6-tris(2-hydroxy-4-octyloxyphenyl)-1,3,5-triazine,2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2,4-bis(2-hydroxy-4-propyloxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triazine,2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(4-methylphenyl)-1,3,5-triazine,2-(2-hydroxy-4-dodecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-(2-hydroxy-4-tridecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-[2-hydroxy-4-(2-hydroxy-3-butyloxy-propoxy)phenyl]-4,6-bis(2,4-dimethyl)-1,3,5-triazine,2-[2-hydroxy-4-(2-hydroxy-3-octyloxy-propyloxy)phenyl]-4,6-bis(2,4-dimethyl)-1,3,5-triazine,2-[4-(dodecyloxy/tridecyloxy-2-hydroxypropoxy-2-hydroxy-phenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-[2-hydroxy-4-(2-hydroxy-3-dodecyloxy-propoxy)phenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-(2-hydroxy-4-hexyloxy)phenyl-4,6-diphenyl-1,3,5-triazine,2-(2-hydroxy-4-methoxyphenyl)-4,6-diphenyl-1,3,5-triazine,2,4,6-tris[2-hydroxy-4-(3-butoxy-2-hydroxy-propoxy)phenyl]-1,3,5-triazine,2-(2-hydroxyphenyl)-4-(4-methoxyphenyl)-6-phenyl-1,3,5-triazine,2-{2-hydroxy-4-[3-(2-ethylhexyl-1-oxy)-2-hydroxypropyloxy]phenyl}-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine.

3. Metal deactivators, for example N,N′-diphenyloxamide,N-salicylal-N′-salicyloyl hydrazine, N,N′-bis(salicyloyl)hydrazine,N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hydrazine,3-salicyloylamino-1,2,4-triazole, bis(benzylidene)oxalyl dihydrazide,oxanilide, isophthaloyl dihydrazide, sebacoyl bisphenylhydrazide,N,N′-diacetyladipoyl dihydrazide, N,N′-bis(salicyloyl)oxalyldihydrazide, N,N′-bis(salicyloyl)thiopropionyl dihydrazide.

4. Phosphites and phosphonites, for example triphenyl phosphite,diphenyl alkyl phosphites, phenyl dialkyl phosphites,tris(nonylphenyl)phosphite, trilauryl phosphite, trioctadecyl phosphite,distearyl pentaerythritol diphosphite,tris(2,4-di-tert-butylphenyl)phosphite, diisodecyl pentaerythritoldiphosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite,bis(2,6-di-tert-butyl-4-methylphenyl)-pentaerythritol diphosphite,diisodecyloxypentaerythritol diphosphite,bis(2,4-di-tert-butyl-6-methylphenyl)pentaerythritol diphosphite,bis(2,4,6-tris(tert-butylphenyl)pentaerythritol diphosphite, tristearylsorbitol triphosphite, tetrakis(2,4-di-tert-butylphenyl)4,4′-biphenylene diphosphonite,6-isooctyloxy-2,4,8,10-tetra-tert-butyl-12H-dibenz-[d,g]-1,3,2-dioxaphosphocin,bis(2,4-di-tert-butyl-6-methylphenyl)methyl phosphite,bis(2,4-di-tert-butyl-6-methylphenyl)ethyl phosphite,6-fluoro-2,4,8,10-tetra-tert-butyl-12-methyl-dibenz[d,g]-1,3,2-dioxaphosphocin,2,2′,2″-nitrilo[triethyltris(3,3′,5,5′-tetra-tert-butyl-1,1′-biphenyl-2,2′-diyl)phosphite],2-ethylhexyl(3,3′,5,5′-tetra-tert-butyl-1,1′-biphenyl-2,2′-diyl)phosphite,5-butyl-5-ethyl-2-(2,4,6-tri-tert-butylphenoxy)-1,3,2-dioxaphosphirane.

5. Hydroxylamines, for example, N,N-dibenzylhydroxylamine,N,N-diethylhydroxylamine, N,N-dioctylhydroxylamine,N,N-dilaurylhydroxylamine, N,N-ditetradecylhydroxylamine,N,N-dihexadecylhydroxylamine, N,N-dioctadecylhydroxylamine,N-hexadecyl-N-octadecylhydroxylamine,N-heptadecyl-N-octadecylhydroxylamine, N,N-dialkylhydroxylamine derivedfrom hydrogenated tallow amine.

6. Nitrones, for example, N-benzyl-alpha-phenyl-nitrone,N-ethyl-alpha-methyl-nitrone, N-octyl-alpha-heptyl-nitrone,N-lauryl-alpha-undecyl-nitrone, N-tetradecyl-alpha-tridcyl-nitrone,N-hexadecyl-alpha-pentadecyl-nitrone,N-octadecyl-alpha-heptadecyl-nitrone,N-hexadecyl-alpha-heptadecyl-nitrone,N-ocatadecyl-alpha-pentadecyl-nitrone,N-heptadecyl-alpha-heptadecyl-nitrone,N-octadecyl-alpha-hexadecyl-nitrone, nitrone derived fromN,N-dialkylhydroxylamine derived from hydrogenated tallow amine.

7. Thiosyneraists, for example, dilauryl thiodipropionate or distearylthiodipropionate.

8. Peroxide scavengers, for example esters of β-thiodipropionic acid,for example the lauryl, stearyl, myristyl or tridecyl esters,rercaptobenziridazole or the zinc salt of 2-mercaptobenzimidazole, zincdibutyldithiocarbamate, dioctadecyl disulfide, pentaerythritoltetrakis(β-dodecylmercapto)propionate.

9. Polyamide stabilisers, for example, copper salts in combination withiodides and/or phosphorus compounds and salts of divalent manganese.

10. Basic co-stabilisers, for example, melamine, polyvinylpyrrolidone,dicyandiamide, triallyl cyanurate, urea derivatives, hydrazinederivatives, amines, polyamides, polyurethanes, alkali metal salts andalkaline earth metal salts of higher fatty acids for example calciumstearate, zinc stearate, magnesium behenate, magnesium stearate, sodiumricinoleate and potassium palmitate, antimony pyrocatecholate or zinkpyrocatecholate.

Compounds from the hydrotalcite series can be described by the generalformula III

M²⁺ _(1−x).M³⁺ _(x).(OH)₂.(A^(y−))_(x/y).pH₂O  (III),

wherein

M²⁺ =Mg, Ca, Sr, Zn, Sn and/or Ni,

M³⁺=Al, B or Bi,

A^(y−) is an anion having the valency y,

y is a number from 1-4,

x is a number from 0-0.5, and

p is a number from 0-20;

further examples are to be found in DE-A-4106403.

A^(y−) is preferably OH⁻, Cl⁻, Br⁻, I⁻, ClO₄ ⁻, HCO₃ ⁻, CH₃COO⁻,C₆H₅COO⁻, CO₃ ²⁻, SO₄ ²⁻, (⁻OOC—COO⁻), (CHOHCOO)₂ ²⁻, (CHOH)₄CH₂OHCOO⁻.C₂H₄(COO)₂ ²⁻, (CH₂COO)₂ ²⁻, CH₃CHOHCOO⁻, SiO₃ ²⁻, SiO₄ ⁴⁻, Fe(CN)₆ ³⁻,Fe(CN)₆ ⁴⁻ or HPO₄ ²⁻.

Other hydrotalcites which may conveniently be used are compounds of thegeneral formula IIIa

M²⁺ _(x).Al₂.(OH)_(2x+6yz).(A^(y−))₂.pH₂O  (IIIa),

in which formula IIIa M²⁺ is at least one metal from the Mg and Znseries, Mg being preferred, and A^(y−) is an anion, for example from theCO₃ ²⁻, (⁻OOC—COO⁻), OH⁻ and S²⁻ series, y is the valency of the anion,p is a positive number, preferably from 0.5 to 15, and x and z arepositive numbers, x preferably being 2 to 6 and z being smaller than 2.

Preferred compounds from the hydrotalcite series are those of thegeneral formula III

M²⁺ _(1−x).M³⁺ _(x).(OH)₂.(A^(y−))_(x/y).pH₂O  (III),

wherein M²⁺ is Mg or a solid solution of Mg and Zn, A^(y−) is CO₃ ², xis a number from 0 to 0.5, and p is a number from 0 to 20.

Particularly preferred hydrotalcites are those of formulae

Al₂P₃.6MgO.CO₂.12H₂O,

Mg_(4.5)Al₂(OH)₁₃.3,5H₂O,

4MgO.Al₂O₃.CO₂.9H₂O,

4MgO.Al₂O₃.CO₂.6H₂O,

ZnO.3MgO.Al₂O₃.CO₂.8-9H₂O or

ZnO.3MgO.Al₂O₃.CO₂.5-6H₂O.

The hydrotalcites can be used in an amount from e.g. 0.1 to 20, usefullyfrom 0.5 to 10 and, preferably, from 0.5 to 5 parts by weight, based on100 parts by weight of the synthetic polymer.

Preferred zeolites are known from “Atlas of Zeolite Structure Types”, W.M. Meier and D. H. Olson, Verlag Butterworths, 2^(nd) edition 1986.

In a broader sense, the zeolites also include aluminium phosphateshaving a zeolite structure.

The preferred zeolites which are known per se have a pore diameter ofaverage effectiveness of 3-5 Å and can be prepared by known methods.Particularly preferred zeolites are those of the NaA type which have apore diameter of average effectiveness of 4 Å, which is why they arealso called zeolites 4A.

Particularly preferred are crystalline sodium alumosilicates, theparticle size of which is at least predominantly in the range from 1-10μ. Particularly preferred zeolites are:

Na₁₂Al₁₂Si₁₂O₄₈.27 H₂O [zeolite A],

Na₆Al₆Si₆O₂₄.2 NaX.7,5 H₂O, X═OH, halogen, ClO₄ [sodalite]

Na₆Al₆Si₃₀O₇₂.24 H₂O,

Na₈Al₈Si₄₀O₉₆.24 H₂O,

Na₁₆Al₁₆Si₂₄O₈₀.16 H₂O,

Na₁₆Al₁₆Si₃₂O₉₆.16 H₂O,

Na₅₆Al₅₆Si₁₃₆O₃₈₄.250 H₂O, [zeolite Y]

Na₈₆Al₈₆Si₁₀₆O₃₈₄.264 H₂O [zeolite X], or those zeolites which can beprepared by partial or complete exchange of the sodium atoms with Li, K,Mg, Ca, Sr or Zn atoms, such as

(Na,K)₁₀Al₁₀Si₂₂O₆₄.20 H₂O.

Ca_(4.5)Na₃[(AlO₂)₁₂(SiO₂)₁₂].30 H₂O

K₉Na₃[(AlO₂)₁₂(SiO₂)₁₂].27 H₂O.

The zeolites can be used in an amount from e.g. 0.1 to 20, convenientlyfrom 0.5 to. 10 and, preferably, from 0.5 to 5 parts by weight, based on100 parts by weight of the synthetic polymer.

11. Benzofuranones and indolinones, for example those disclosed in U.S.Pat. No. 4,325,863; U.S. Pat. No. 4,338,244; U.S. Pat. No. 5,175,312;U.S. Pat. No. 5,216,052; U.S. Pat. No. 5,252,643; DE-A-4316611;DE-A-4316622; DE-A-4316876; EP-A-0589839 or EP-A-0591102 or3-[4-(2-acetoxyethoxy)phenyl]-5,7-di-tert-butyl-benzofuran-2-one,5,7-di-tert-butyl-3-[4-(2-stearoyloxyethoxy)phenyl]benzofuran-2-one,3,3′-bis[5,7-di-tert-butyl-3-(4-[2-hydroxyethoxy]phenyl)benzofuran-2-one],5,7-di-tert-butyl-3-(4-ethoxyphenyl)benzofuran-2-one,3-(4-acetoxy-3,5-dimethylphenyl)-5,7-di-tert-butyl-benzofuran-2-one,3-(3,5-dimethyl-4-pivaloyloxyphenyl)-5,7-di-tert-butylbenzofuran-2-one,3 3-(2,3-dimethylphenyl)-5,7-di-tert-butyl-benzofuran-2-one.

Interesting compositions are those, wherein component (b) is astabiliser selected from the group consisting of phenolic antioxidants,aminic antioxidants, UV absorbers, light stabilisers, metaldeactivators, phosphites, phosphonites, hydroxylamines, nitrones,thiosynergists, peroxide-scavenging compounds, compounds of thebenzofuran-2-one type and/or PVC heat stabilisers, such asMe(II)-carboxylates, Me(II) signifying Ba, Ca, Mg or Zn, preferablymixtures of Ba/Zn- or Ca/Zn-carboxylates.

Examples of nucleating agents are described in R. Gächter and H. Müller,Hanser Verlag, 3^(rd) edition, 1990, pages 863-875. Particularlyinteresting are benzenesulfonamides, bis(p-ethylbenzylidene)sorbitol,sodium benzoate, sodium bicarbonate,sodium-2-2′-methylenebis(4,6-di-tert-butylphenyl)phosphate, or compoundsof formula I

wherein R₁, R₂, R₃ and R₄ are each independently of one another hydrogenor C₁-C₄alkyl.

Alkyl containing 1 to 4 carbon atoms is a branched or unbranchedradical, for example methyl, ethyl, n-propyl, isopropyl, n-butyl,isobutyl or tert-butyl. One of the preferred meanings of R₁, R₂, R₃ andR₄ is methyl.

Particularly preferred compositions are those, wherein the nucleatingagent is a compound of formula Ia (Irgaclear®DM), Ib (Irgaclear®D) or Ic(Millad®3988).

Irgaclear®DM and Irgaclear®D are registered trademarks of CibaSpezialitätenchemie AG. Millad®3988 is a registered trademark ofMiliken.

Of particular interest are those compositions, wherein the nucleatingagent is a mixture of Irgaclear®DM and sodium benzoate.

Examples of flame retardants are described in R. Gächter and H. Müller,Hanser Verlag, 3^(rd) edition, 1990, pages 709-747. Particularlyinteresting flame retardants are those selected from the groupconsisting of tetraphenyl-resorcinol-diphosphite (Fyrolflex® RDP, AkzoNobel), chloroalkyl-phosphate ester (Antiblaze®AB-100, Albright &Wilson; Fyrol® FR-2, Akzo Nobel), polybrominated diphenyl oxide (DE-60F,Great Lakes Corp.), decabromodiphenyl oxide.(DBDPO; Saytex® 102E),antimonium trioxide (Sb₂O₃), antimonium peentoxide (Sb₂O₅),tris[3-bromo-2,2-(bromomethyl)propyl]phosphate (PB 370®, FMC Corp.),triphenyl phosphate, bis(2,3-dibromopropyl ether) of bisphenol A (PE68),ammonium polyphosphate (APP) or (Hostaflam® AP750), oligomericresorcinol-diphosphate (RDP), brominated epoxy resin,ethylenebis(tetrabromophthalimide) (BT93),bis(hexachlorocyclopentadiene)cyclooctane (Declorane plus®), calciumsulfate, chlorinated paraffin, magnesium carbonate, melamine phosphate,melamine pyrophosphate, molybdenum trioxide, zinc oxide,1,2-bis(tribromophenoxy)ethane (FF680), tetrabromobisphenol A (Saytex®RB100), magnesium hydroxide, aluminium trihydrate, zinc borate,ethylenediamine diphosphate (EDAP), and compounds of formula F1

wherein

G₁ and G₂ are each independently of the other C₁-C₄alkyl or together arepentamethylene, E is C₁-C₁₈alkoxy, C₅-C₁₂cycloalkoxy, C₇-C₂₅aralkoxy orC₆-C₁₂aryloxy, and Z₁ and Z₂ are methyl, or Z₁ and Z₂ together form aring which may be additionally substituted by an ester, ether, amide,amino, carboxy or urethane group. The compounds of formula F1 are alsocalled NOR compounds and are disclosed in WO-A-99/00450.

Polymeric dispersing or solvating agents having amphiphilic propertiesare polymeric dispersing or solvating agents which have polar andnonpolar groups in the same molecule and they are, for example,dispersing or solvating agents based on polyethylene glycols (PEG),polyacrylates, polysiloxanes, polyvinyl acetate or block copolymerscontaining at least one block copolymer based on acrylate, acrylic acidor methacrylate.

The novel polymeric dispersing or solvating agents having amphiphilicproperties have at least two different polarities within one polymermolecule. Oligomeric structures are also possible. They are usuallycopolymers, for example random copolymers, or block copolymers which canbe prepared by known polymerisation reactions, for example by radical oranionic polymerisation, by polycondensation reactions, such as byreaction of end-functionalised oligomeric or comb polymers, whichpolymers may be prepared e.g. by graft reaction. Block copolymers are,for example, diblock copolymers (A—B type) or triblock copolymers (A—B—Aor A—B—C type) and so-called tapered structures.

Diblock copolymers (A—B type) are, for example,poly(styrene-b-methylmethacrylate),poly(styrene-b-tert-butylmethacrylate), poly(styrene-b-methylacrylate),poly(styrene-b-n-butylacrylate), poly(styrene-b-tert-butylacrylate),poly(styrene-b-butadiene), poly(styrene-b-isoprene[1,4-addition]),tapered block copolymer poly(styrene-b-butadiene), tapered blockcopolymer poly(styrene-b-ethylene), poly(styrene-b-2-vinylpyridine),poly(styrene-b-4-vinylpyridine), poly(styrene-bis-tert-butylstyrene),poly(styrene-b-dimethylsiloxane), poly(butadiene-bdimethylsiloxane),poly(butadiene[1,4-addition]-b-methylmethacrylate),poly(isoprene[1-4-addition]-b-methylmethacrylate),poly(butadiene-b-tert-butylmethacrylate),poly(butadiene-b-tert-butylacrylate), poly(isoprene-b-2-vinylpyridine),poly(butadiene-b-4-vinylpyridine), poly(styrene-b-methylmethacrylate),poly(methylmethacrylate-b-tert-butylmethacrylate),poly(methylmethacrylate-b-tert-butylacrylate),poly(tert-butylacrylate-b-methylmethacrylate),poly(n-butylacrylate-b-methylmethacrylate),poly(2-vinylpyridine-b-methylmethacrylate),poly(tert-butylmethacrylate-b-tert-butylacrylate),poly(tert-butylmethacrylate-b-2-vinylpyridine),poly(tert-butylmethacrylate-b-4-vinylpyridine),poly(tert-butylacrylate-b-2-vinylpyridine),poly(2-vinylpyridine-b-4-vinylpyridine),poly(ethylene-b-methylmethacrylate), poly(ethylene-b-2-vinylpyridine) orpoly(ethylene-b-4-vinylpyridine).

Triblock copolymers of the A—B—A type are, for example,poly(methylmethacrylate-b-styrene-b-methylmethacrylate),poly(tert-butylmethacrylate-b-styrene-b-tert-butylmethacrylate),poly(tert-butylacrylate-b-styrene-b-tert-butylacrylate),poly(2-vinylpyridine-b-styrene-b-tert-butylacrylate),poly(4-vinylpyridine-b-styrene-b-4-vinylpyridine),poly(butadiene[1,2-addition]-b-styrene-b-butadiene[1,2-addition]),poly(butadiene[1,4-addition]-b-styrene-b-butadiene[1,4-addition]),poly(styrene-b-butadiene[1,4- and 1,2-addition]-b-styrene),poly(methylmethacrylate-b-butadiene[1,4- or1,2-addition]-b-methylmethacrylate),poly(tert-butyl-methacrylate-b-methylmethacrylate-b-tert-butylmethacrylate),poly(tert-butylacrylate-b-methylmethacrylate-b-tertbutylacrylate),poly(methylmethacrylate-b-2-vinylpyridine-b-methylmethacrylate),poly(4-vinylpyridine-b-methylmethacrylate-b-4-vinylpyridine),poly(methylmethacrylate-b-tert-butylacrylate-b-methylmethacrylate),poly(methylmethacrylate-b-n-butylacrylate-b-methylmethacrylate),poly(tert-butylmethacrylate-b-tert-butylacrylate-b-tert-butylmethacrylate),poly(2-vinylpyridine-b-tert-butylacrylate-b-2-vinylpyridine),poly(4-vinylpyridine-b-tert-butylacrylate-b-4-vinylpyridine),poly(styrene-b-n-butylacrylate-b-styrene),poly(styrene-b-ethylacrylate-b-styrene),poly(styrene-b-ethylene-b-styrene), poly(styrene-b-butylene-b-styrene),poly(ethylene oxide-b-styrene-b-ethylene oxide), poly(styrene-b-ethyleneoxide-b-styrene) or poly(styrene-b-acrylic acid-b-styrene).

Triblock copolymers of the A—B—C type are, for example,poly(styrene-b-butadiene-b-2-vinylpyridine),poly(styrene-b-butadiene-b-4-vinylpyridine),poly(styrene-b-tert-butylmethacrylate-b-2-vinylpyridine),poly(styrene-b-tert-butyimethacrylate-b-4-vinylpyridine),poly(styrene-b-2-vinylpyridine-b-4-vinylpyridine),poly(butadiene-b-styrene-b-methylmethacrylate),poly(styrene-b-butadiene-b-methylmethacrylate),poly(styrene-b-2-vinylpyridine-b-ethyl oxide),poly(styrene-b-tert-butylacrylate-b-methylmethacrylate), poly(styreneacid-b-methylmethacrylate),poly(styrene-b-a-methylstyrene-b-methylmethacrylate) orpoly(styrene-b-amethylstyrene-b-tert-butylacrylate).

Long-chain block copolymers of particular interest have a chain lengthof more than 10 carbon atoms, preferably of C₁₂-C₁₈carbon atoms.

Particularly suitable dispersing or solvating agents having amphiphilicproperties are, for example, poly(butadienemethylmethacrylate),poly(isoprenemethylmethacrylate), poly(ethylenemethylmethacrylate),poly(styrene-4-vinylpyridine), poly(styrene-2-vinylpyridine),poly(styrene-n-butylacrylate), poly(styrene-tert-butylacrylate),poly(styrene sodium acrylate), poly(styrene-acrylic acid),poly(methylmethacrylate sodium acrylate), poly(methylmethacrylate sodiummethacrylate), poly(ethylene oxide-ε-caprolactone), poly(2-vinylpyridineethylene oxide), poly(butadiene-ethylene oxide), poly(butadiene sodiumacrylate), poly(ethylene-ethylene oxide), poly(ethylene-propyleneoxide), poly(styrene-ethylacrylate-styrene), poly(ethyleneoxide-styrene′-ethylene oxide), poly(styrene-acrylic acid-styrene),poly(styrenebutadienemethyimethacrylate),poly(styrene-vinylpyridine-ethylene oxide), poly(styrene-4-vinylbenzoicacid), poly(styrene-polyglycidyl-methacrylate), poly(ethylene-glycidylmethacrylate), poly(propylene acrylic acid), poly(ethylene acrylicacid), poly(propylenemaleic anhydride), poly(ethylenemaleic anhydride),poly(styrenemaleic anhydride), polymethacrylic acid-polyalkylene; oxideblock copolymers for example according to EP-A-0 859 028,polysiloxanepolyoxyalkylene, copolymers of maleates and styrene orstyrene derivatives, for example according to EP-A-0 791 024,polystyrene-polysiloxane block copolymers, polyacrylatepolysiloxaneblock copolymers and cyclosiloxane-radiale copolymers, prepared e.g.using ATRP technology according to EP-A-0 870 774,methylacrylate-styrene copolymer, methylmethacrylate-styrene;polybutadiene-methylacrylates, prepared by nitroxyl-initiated radicalpolymerisation according to EP-A-0 135 280.

The polyalkylene oxides are preferably polyethylene oxide, polypropyleneoxide and polybutylene oxide.

Suitable block copolymers are, for example, polyacrylate/polystyrene,polymethacrylatelpolyethylene oxide, polyacrylate/polyethylene oxide,polyacrylatelpolyethylene, polyvinyl acetate/polyethylene,polystyrene/polybutadiene, polyacrylate/polybutadiene,polyacrylate/polyisoprene, polyisoprene/polymethylmethacrylate,polyethylene/polymethylmethacrylate, polyethylenelpolyethylene oxide orpolyethylenelpolypropylene oxide.

Particularly suitable dispersing or solvating agents having amphiphilicproperties are, for example, poly(styrene-bis-sodium acrylate),poly(styrene-bis-acrylic acid), poly(styrene-bis-sodium methacrylate),poly(styrene-bis-N-methyl-4-vinylpyridinium iodide),poly(isoprene-bis-N-methyl-2-vinylpyridinium iodide),poly(styrene-bis-ethylene oxide), poly(methylmethacryate-bis-sodiumacrylate), poly(methylmethacrylate-bis-sodium methacrylate),poly(methylmethacrylate-bis-ethylene oxide),poly(tert-butylmethacrylate-bis-ethylene oxide),poly(methylmethacrylate-bis-N-methyl-4-vinylpyridinium iodide),poly(ethylene oxide-bis-lactate), poly(2-vinylpyridine-bis-ethyleneoxide), poly(butadiene-bis-sodium acrylate), poly(butadiene-bis-sodiummethacrylate), poly(butadiene-bis-N-methyl-4-vinylpyridinium iodide),poly(butadiene-bisethylene oxide), poly(ethylene-bis-ethylene oxide) orpoly(ethylene-bis-propylene oxide).

Particularly preferred polysiloxanes containing long-chain side groupsare disclosed, inter alia, in U.S. Pat. No. 5,387,467.

Other likewise preferred dispersing or solvating agents based onpolyacrylates are described, inter alia, in U.S. Pat. No. 5,133,898.

Particularly preferred dispersing or solvating agents based on acrylateare, for example, Tegomer®DA 100, Tegome®DA 102 or Wax P 121®, of Th.Goldschmidt AG, Germany.

Particularly preferred are compositions wherein component (c) is adispersing or solvating agent based on polyacrylates or polysiloxanescontaining long-chain side-groups.

The blend of components (b) and (c) is suitable for stabilisingsynthetic polymers, in particular thermoplastic polymers, e.g.polyolefins and polystyrenes, against oxidative, thermal orlight-induced degradation.

Examples of synthetic polymers are:

1. Polymers of monoolefins and diolefins, for example polypropylene,polyisobutylene, polybut-1-ene, poly-4-methylpent-1-ene, polyisoprene orpolybutadiene, as well as polymers of cycloolefins, for instance ofcyclopentene or norbornene, polyethylene (which optionally can becrosslinked), for example high density polyethylene (HDPE), high densityand high molecular weight polyethylene (HDPE-HMW), high density andultrahigh molecular weight polyethylene (HDPE-UHMW), medium densitypolyethylene (MDPE), low density polyethylene (LDPE), linear low densitypolyethylene (LLDPE), (VLDPE) and (ULDPE).

Polyolefins, i.e. the polymers of monoolefins exemplified in thepreceding paragraph, preferably polyethylene and polypropylene, can beprepared by different, and especially by the following, methods:

a) radical polymerisation (normally under high pressure and at elevatedtemperature).

b) catalytic polymerisation using a catalyst that normally contains oneor more than one metal of groups IVb, Vb, VIb or VIII of the PeriodicTable. These metals usually have one or more than one ligand, typicallyoxides, halides, alcoholates, esters, ethers, amines, alkyls, alkenylsand/or aryls that may be either π- or σ-coordinated. These metalcomplexes may be in the free form or fixed on substrates, typically onactivated magnesium chloride, titanium(III) chloride, alumina or siliconoxide. These catalysts may be soluble or insoluble in the polymerisationmedium. The catalysts can be used by themselves in the polymerisation orfurther activators may be used, typically metal alkyls, metal hydrides,metal alkyl halides, metal alkyl oxides or metal alkyloxanes, saidmetals being elements of groups Ia, IIa and/or IIIa of the Periodic.Table. The activators may be modified conveniently with further ester,ether, amine or silyl ether groups. These catalyst systems are usuallytermed Phillips, Standard Oil Indiana, Ziegler (-Natta), TNZ (DuPont),metallocene or single site catalysts (SSC).

2. Mixtures of the polymers mentioned under 1), for example mixtures ofpolypropylene with polyisobutylene, polypropylene with polyethylene (forexample PP/HDPE, PP/LDPE) and mixtures of different types ofpolyethylene (for example LDPE/HDPE).

3. Copolymers of mono6lefins and diolefins with each other or with othervinyl monomers, for example ethylene/propylene copolymers, linear lowdensity polyethylene (LLDPE) and mixtures thereof with low densitypolyethylene (LDPE), propylene/but-1-ene copolymers,propylene/isobutylene copolymers, ethylene/but-1-ene copolymers,ethylene/hexene copolymers, ethylene/methylpentene copolymers,ethylene/heptene copolymers, ethylene/octene copolymers,propylene/butadiene copolymers, isobutylene/isoprene copolymers,ethylene/alkyl acrylate copolymers, ethylene/alkyl methacrylatecopolymers, ethylene/vinyl acetate copolymers and their copolymers withcarbon monoxide or ethylene/arylic acid copolymers and their salts(ionomners) as well as terpolymers of ethylene with propylene, and adiene such as hexadiene, dicyclopentadiene or ethylidene-norbornene; andmixtures of such copolymers with one another and with polymers mentionedin 1)) above, for example polypropylene/ethylene-propylene copolymers,LDPE/ethylene-vinyl acetate copolymers (EVA), LDPE/ethylene-acrylic acidcopolymers (EAA), LLDPE/EVA, LLDPE/EAA and alternating or randompolyalkylene/carbon monoxide copolymers and mixtures thereof with otherpolymers, for example polyamides.

4. Hydrocarbon resins (for example C₅-C₉) including hydrogenatedmodifications thereof (e.g. tackifiers) and mixtures of polyalkylenesand starch.

5. Polystyrene, poly(p-methylstyrene), poly(α-methylstyrene).

6. Copolymers of styrene or α-methylstyrene with dienes or acrylicderivatives; for example styrene/butadiene, styrene/acrylonitrile,styrene/alkyl methacrylate, styrene/butadiene/alkyl acrylate,styrene/butadiene/alkyl methacrylate, styrehe/maleic anhydride,styrene/acrylonitrile/methyl acrylate; mixtures of high impact strengthof styrene copolymers and another polymer, for example a polyacrylate, adiene polymer or an ethylene/propylene/diene terpolymer; and blockcopolymers of styrene such as styrene/butadiene/styrene,styrenelisoprene/styrene, styrene/ethylene/butylene/styrene orstyrene/ethylene/propylene/styrene.

7. Graft copolymers of styrene or α-methylstyrene, for example styreneon polybutadiene, styrene on polybutadiene-styrene orpolybutadiene-acrylonitrile copolymers; styrene and acrylonitrile (ormethacrylonitrile) on polybutadiene; styrene, acrylonitrile and methylmethacrylate on polybutadiene; styrene and maleic anhydride onpolybutadiene; styrene, acrylonitrile and maleic anhydride or maleimideon polybutadiene; styrene and maleimide on polybutadiene; styrene andalkyl acrylates or methacrylates on polybutadiene; styrene andacrylonitrile on ethylene/propylene/diene terpolymers; styrene andacrylonitrile on polyalkyl acrylates or polyalkyl methacrylates, styreneand acrylonitrile on acrylatelbutadiene copolymers, as well as mixturesthereof with the copolymers listed under 6), for example the copolymermixtures known as ABS, MBS, ASA or AES polymers.

8. Halogen-containing polymers such as polychloroprene, chlorinatedrubbers, chlorinated and brominated copolymer of isobutylene-isoprene(halobutyl rubber), chlorinated or sulfochlorinated polyethylene,copolymers of ethylene and chlorinated ethylene, epichlorohydrin homo-and copolymers, especially polymers of halogen-containing vinylcompounds, for example polyvinyl chloride, polyvinylidene chloride,polyvinyl fluoride, polyvinylidene fluoride, as well as copolymersthereof such as vinyl chloride/vinylidene chloride, vinyl chloride/vinylacetate or vinylidene chloride/vinyl acetate copolymers.

9. Polymers derived from α,β-unsaturated acids and derivatives thereofsuch as polyacrylates and polymethacrylates; polymethyl methacrylates,polyacrylamides and polyacrylonitriles, impact-modified with butylacrylate.

10. Copolymers of the monomers mentioned under 9) with each other orwith other unsaturated monomers, for example acrylonitrile/butadienecopolymers, acrylonitrile/alkyl acrylate copolymers,acrylonitrile/alkoxyalkyl acrylate or acrylonitrile/vinyl halidecopolymers or acrylonitrile/alkyl methacrylate/butadiene terpolymers.

11. Polymers derived from unsaturated alcohols and amines or the acylderivatives or acetals thereof, for example polyvinyl alcohol, polyvinylacetate, polyvinyl stearate, polyvinyl benzoate, polyvinyl maleate,polyvinyl butyral, polyallyl phthalate or polyallyl melamine; as well astheir copolymers with olefins mentioned in 1) above.

12. Homopolymers and copolymers of cyclic ethers such as polyalkyleneglycols, polyethylene oxide, polypropylene oxide or copolymers thereofwith bisglycidyl ethers.

13. Polyacetals such as polyoxymethylene and those polyoxymethyleneswhich contain ethylene oxide as a comonomer; polyacetals modified withthermoplastic polyurethanes, acrylates or MBS.

14. Polyphenylene oxides and sulfides, and mixtures of polyphenyleneoxides with styrene polymers or polyamides.

15. Polyurethanes derived from hydroxyl-terminated polyethers,polyesters or polybutadienes on the one hand and aliphatic or aromaticpolyisocyahates on the other, as well as precursors thereof.

16. Polyamides and copolyamides derived from diamines and dicarboxylicacids and/or from aminocarboxylic acids or the corresponding lactams,for example polyamide 4, polyamide 6, polyamide 6/6, 6/10, 6/9, 6/12,4/6, 12/12, polyamide 11, polyamide 12, aromatic polyamides startingfrom m-xylene diamine and adipic acid; polyamides prepared fromhexamethylenediamine and isophthalic or/and terephthalic acid and withor without an elastomer as modifier, for examplepoly-2,4,4,-trimethylhexamethylene terephthalamide or poly-m-phenyleneisophthalamide; and also block copolymers of the aforementionedpolyamides with polyolefins, olefin copolymers, ionomers or chemicallybonded or grafted elastomers; or with polyethers, e.g. with polyethyleneglycol, polypropylene glycol or polytetramethylene glycol; as-well aspolyamides or copolyamides modified with EPDM or ABS; and polyamidescondensed during processing (RIM polyamide systems).

17. Polyureas, polyimides, polyamide-imides, polyetherimids,polyesterimids, polyhydantoins and polybenzimidazoles.

18. Polyesters derived from dicarboxylic acids and diols and/or fromhydroxycarboxylic acids or the corresponding lactones, for examplepolyethylene terephthalate, polybutylene terephthalate,poly-1,4-dimethylolcyclohexane terephthalate, polyalkylene naphthalate(PAN) and polyhydroxybenzoates, as well as block copolyether estersderived from hydroxyl-terminated polyethers; and also polyestersmodified with polycarbonates or MBS.

19. Polycarbonates and polyester carbonates.

20. Polysulfones, polyether sulfones and polyether ketones.

21. Crosslinked polymers derived from aldehydes on the one hand andphenols, ureas and melamine's on the other hand, such asphenol/formaldehyde resins urea/formaldehyde resins andmelamine/formaldehyde resins.

22. Drying and non-drying alkyd resins.

23. Unsaturated polyester resins derived from copolyesters of saturatedand unsaturated dicarboxylic acids with polyhydric alcohols and vinylcompounds as crosslinking agents, and also halogen-containingmodifications thereof of low flammability.

24. Crosslinkable acrylic resins derived from substituted acrylates, forexample epoxy acrylates, urethane acrylates or polyester acrylates.

25. Alkyd resins, polyester resins and acrylate resins crosslinked withmelamine resins, urea resins, isocyanates, isocyanurates,polyisocyanates or epoxy resins.

26. Crosslinked epoxy resins derived from aliphatic, cycloaliphatic,heterocyclic or aromatic glycidyl compounds, e.g. products, ofdiglycidyl ethers of bisphenol A and bisphenol F, which are crosslinkedwith customary hardeners such as anhydrides or amines, with or withoutaccelerators.

27. Natural polymers such as cellulose, rubber, gelatin and chemicallymodified homologous derivatives thereof, for example cellulose acetates,cellulose propionates and cellulose butyrates, or the cellulose etherssuch as methyl cellulose; as well as rosins and their derivatives.

28. Blends of the aforementioned polymers (polyblends), for examplePP/EPDM, Polyamide/EPDM or ABS, PVC/EVA, PVC/ABS, PVC/MBS, PC/ABS,PBTP/ABS, PC/ASA, PC/PBT, PVC/CPE, PVC/acrylates, POM/thermoplastic PUR,PC/thermoplastic PUR, POM/acrylate, POM/MBS, PPO/HIPS, PPO/PA 6.6 andcopolymers, PANHDPE, PA/PP, PA/PPO, PBT/PC/ABS or PBT/PET/PC.

A preferred group of synthetic polymers are halogen-containing polymers.These are preferably chlorine-containing polymers, for example polymersof vinyl chloride, vinyl resins containing vinyl chloride units in theirstructure, copolymers of vinyl chloride, and vinyl esters of aliphaticacids, in particular vinyl acetate, copolymers of vinyl chloride withesters of acrylic and methacrylic acid and with acrylonitrile,copolymers of vinyl chloride with diene compounds and unsaturateddicarboxylic acids or their anhydrides, copolymers of vinyl chloridewith diethylmaleate, diethylfumarate or maleic anhydride,postchlorinated polymers and copolymers of vinyl chloride, copolymers ofvinyl chloride and vinylidene chloride with unsaturated aldehydes,ketones and others, such as acrolein, crotonic aldehyde, vinyl methylketone, vinyl methyl ether, vinyl isobutyl ether and similar compounds;polymers of vinylidene chloride and copolymers thereof with vinylchloride and other polymerisable compounds; polymers of vinylchloroacetate and dichlorodivinyl ether; chlorinated polymers of vinylacetate, chlorinated polymeric esters of acrylic acid and ofalpha-substituted acrylic acid; polymers of chlorinated styrenes, forexample dichlorostyrene; chlorinated rubbers; chlorinated polymers ofethylene; polymers and postchlorinated polymers of chlorobutadiene andtheir copolymers with vinyl chloride, rubber hydrochloride andchlorinated rubber hydrochloride; and blends of the cited polymers witheach other or with other polymerisable compounds.

Also included are the graft polymers of PVC with EVA, ABS and MBS.Preferred substrates are also blends of the above-cited homo- andcopolymers, in particular vinyl chloride homopolymers, with otherthermoplastic or/and elastomeric polymers, in particular blends withABS, MBS, NBR, SAN, EVA, CPE, MBAS, PMA, PMMA, EPDM and polylactones.

Other preferred polymers are suspension and bulk polymers, and emulsionpolymers.

The chlorine-containing polymer is particularly preferably polyvinylchloride, especially suspension polymers and bulk polymers.

The chlorine-containing polymers preferably do not contain anyplasticiser.

It is preferred to use a stabilised halogen-containing polymer, asdescribed above, containing at least one inorganic zinc compound, suchas zinc oxide, zinc hydroxide, zinc chloride, zinc sulfide or superbasiczinc oxidyhydroxide addition compounds, or an organic zinc compound fromthe series of the aliphatic saturated C₂-C₂₂carboxylates, of thealiphatic unsaturated C₃-C₂₂carboxylates, of the aliphaticC₂-C₂₂carboxylates, which are substituted by at least one OH group orthe chain of which is interrupted by at least one 0 atom (oxa acids), ofthe cyclic and bicycliccarboxylates containing 5-22 carbon atoms, of thephenylcarboxylates which are unsubstituted or substituted by at leastone OH group and/or by C₁-C₁₆alkyl, of the naphthylcarboxylates whichare unsubstituted or substituted by at least one OH group and/or byC₁-C₁₆alkyl, of the phenyl-C₁-C₁₆alkylcarboxylates, of thenaphthyl-C₁-C₁₆alkylcarboxylates or of the phenolates which may besubstituted by C₁-C₁₂alkyl.

Examples to be mentioned by name are the zinc salts of the monovalentcarboxylic acids, such as acetic acid, propionic acid, butyric acid,valenc acid, hexanoic acid, oenanthic acid, octanoic acid, neodecanoicacid, 2-ethylhexanoic acid, pelargonic acid, decanoic acid, undecanoicacid, dodecanoic acid, tridecanoic acid, myristylic acid, paclmiticacid, isostearic acid, stearic acid, 12-hydroxystearic acid,9,10-dihydroxystearic acid, 3,6-dioxaheptanoic acid,3,6,9-trioxadecanoic acid, behenic acid, behzoic acid,p-tert-butylbenzoic acid, dimethylhydroxybenzoic acid,3,5-di-tert-butyl-4-hydroxybenzoic acid, tolylic acid, dimethylbenzoicacid, ethylbenzoic acid, n-propylbenzoic acid, salicylic acid,p-tert-octylsalicylic acid and sorbic acid; the zinc salts of themonoesters of divalent carboxylic acids, such as oxalic acid, malonicacid, succinic acid, glutaric acid, adipic acid, fumaric acid,pentane-1,5-dicarboxylic acid, hexane-1,6-dicarboxylic acid,heptane-1,7-dicarboxylic acid, octane-1,8-dicarboxylic acid,3,6,9-trioxadecane-1,10-dicarboxylic acid, polyglycol dicarboxylic acid(n=10-12), phthalic acid, isophthalic acid, terephthalic acid andhydroxyphthalic acid; and of the di- or triesters of tri-ortetravalentcarboxylic acids, such as hemimellitic acid, trimellitic acid,pyromellitic acid, citric acid, and the zinc salts of the mono- anddi-esterified phosphoric acid or of the monoesterified phosphorousacids, such as described in JP3,275,570.

Particularly preferred is an organic zinc carboxylate of a carboxylicacid containing 7 to 18 carbon atoms (zinc soaps), for example benzoatesor alkanoates, preferably stearate, oleate, laurate, palmitate,behenate, hydroxystearates; dihydroxystearates or (iso)octanoate.Stearate, oleate, benzoate and 2-ethylhexanoate are very particularlypreferred.

Other suitable compounds besides the cited zinc compounds are alsoinorganic or organic aluminium compounds to which the specificationsgiven above for the zinc compounds also apply. Further details on theusable and preferred aluminium compounds are to be found in U.S. Pat.No. 4,060,512.

Other suitable compounds besides the cited zinc compounds are alsoinorganic or organic rare-earth compounds, to which the specificationsgiven above for the zinc compounds apply. The term rare-earth compoundis to be understood as meaning especially compounds of the elementscerium, praseodym, neodym, samarium, europium, gadolinium, terbium,dysprosium, holmium, erbium, thulium, ytterbium, lutetium, lanthanum andyttrium, mixtures with cerium being particularly preferred. Otherpreferred rare-earth compounds are to be found in EP-A-0 108 023.

Where appropriate, it is possible to use a mixture of zinc, aluminium,lanthanum or lanthanoid compounds of different structure. It is alsopossible for organic zinc, aluminium, lanthanum or lahthanoid compoundsto be coated onto a hydrotalcite, zeolite or dawsonite; see also DE-A-4031 818.

The PVC stabilised according to this invention may contain additionaladditives. These additional additives are, for example, inorganic ororganic calcium or magnesium compounds, zeolites, hydrotalcites,dawsonites, magadiites, kenyaites, canemite, 1,3-diketo compounds,polyols, N-containing compounds, for example β-aminocrotonates, such asmentioned in EP-A-0 465 405, page 6, lines 9-14; α-phenylindole,pyrroles, sterically hindered amines (HALS), dihydropyridines and theirpolymers, perchlorates, epoxides, phenolic antioxidants, naphthenes,thiophosphates, plasticisers, fillers and reinforcing agents, such ascalcium carbonate, magnesium oxide, magnesium hydroxide, silicates,glass fibres, talcum, kaolin, chalk, mica, metal oxides and metalhydroxides, carbon black or graphite; phosphites, sequestering agents,light stabilisers, UV absorbers, lubricants, impact modifiers andprocessing agents, fatty acid esters, paraffins, blowing agents,fluorescent whitening agents, gelling agents, colourants, pigments,smoke suppressants, antistatic agents, antifogging agents, biocides,thiodipropionic acids and their esters, dialkyldisulfides,mercaptocarboxylates, peroxide-scavenging compounds, modifiers andfurther complex formers for Lewis acids.

Preferred synthetic polymers are also polyolefins and polystyrenes, inparticular polyethylene or polypropylene.

To be highlighted in particular is the effect of the blend of thecomponents (b) and (c) against oxidative and thermal degradation ofpolyolefins which occurs when thermoplasts are processed and used. Theinventive components (b) and (c) are therefore excellently suitable foruse as long-term heat stabilisers.

Component (b) is preferably added to the synthetic polymer to bestabilised in an amount from 0.01 to 10%, for example from 0.01 to 5%,preferably from 0.025 to 3%, particularly preferably from 0.025 to 1%,based on the weight of the synthetic polymer to be stabilised.

Component (c) is usefully added to the synthetic polymer to bestabilised in an amount from 0.005 to 10%, preferably from 0.01 to 5%,for example from 0.02 to 1%, based on the weight of the syntheticpolymer to be stabilised.

In addition to the component (b) and (c), the novel compositions cancontain further costabilisers (additives), for example fillers andreinforcing agents, plasticisers, lubricants, emulsifiers, pigments,rheology additives, catalysts, flow control agents, fluorescentwhitening agents, flame retardants or blowing agents.

Fillers and reinforcing agents are, for example, calcium carbonate,silicates, glass fibres, glass beads, talcum, kaolin, mica, bariumsulfate, metal oxides and metal hydroxides, carbon black, graphite, woodflour, and flours or fibres of other natural products, or syntheticfibres.

Particularly interesting compositions are-those which comprise inaddition to components (a), (b) and (c) as further additives fillers, inparticular talcum, kaolin, mica or calcium carbonate.

The fillers and reinforcing agents, such as talcum, calcium carbonate orkaolin, are added to the polyolefins in concentrations of, for example,0.01 to 40%, based on the total weight of the polyolefins to bestabilised.

Other interesting additional additives in the novel compositions arealso alkaline earth metal salts of higher fatty acids, such as calciumstearate or alkaline earth metal salts of lactic acids, for examplecalcium lactylate or calcium stearoyl-2-lactylate.

The components (b) and (c) and further optional additives areincorporated into the synthetic polymer by known methods, for examplebefore or during extrusion or moulding or also by applying the dissolvedor dispersed stabiliser blend to the synthetic polymer, if required withsubsequent evaporation of the solvent. The additive blend of thecomponents (b) and (c) and further optional additives can also be addedto the polymers to be stabilised in the form of a masterbatch containingthem e.g. in a concentration of 2.5 to 25% by weight.

The additive blend of the components (b) and (c) and further optionaladditives can also be added before or during the polymerisation orbefore crosslinking.

The additive blend of the components (b) and (c) and further optionaladditives can be incorporated into the synthetic polymer to bestabilised in pure form or encapsulated in waxes, oils or polymers.

The additive blend of the components (b) and (c) and further optionaladditives can also be sprayed onto the synthetic polymer to bestabilised. This blend is capable of diluting other additives (e.g. theabove-mentioned standard additives) or their melts so that it can alsobe sprayed onto the synthetic polymer to be stabilised together withthose additives. The addition by spraying is particularly advantageousduring the deactivation of the polymerisation catalysts, it beingpossible to use e.g. the steam used for deactivation for spraying.

In the case of spherical polymerised polyolefins it may for example beadvantageous to apply the additive blend by spraying onto the components(b) and (c), optionally together with other additives.

The synthetic polymers thus stabilised can be used in a wide range offorms, for example as foils, fibres, filaments, moulding compositions,profiles or as binders for paint systems, in particular powder coatingcompositions, adhesives or putties.

The polyolefins stabilised in this manner can also be used in a widerange of forms, in particular as high-build polyolefin moulded articleswhich are in permanent contact with extracting media, for example tubesfor liquids or gases, foils, fibres, geomembranes, filaments, profilesor tanks.

The preferred high-build polyolefin moulded articles have a coatingthickness from 1 to 50 mm, preferably from 1 to 30 mm, e.g. from 2 to 10mm.

A preferred embodiment of this invention is therefore the use of thecomponent (c) for the improved dispersion, in particular for thedissolution or compatibility enhancement, of additives selected from thestabiliser, antistatic agent, nucleating agent, biocide and/or flameretardant group in synthetic polymers.

Another preferred embodiment of this invention is also the use of theadditive blend of the components (b) and (c) for stabilising syntheticpolymers against oxidative, thermal or light-induced degradation, withthe proviso that component (b) contains at least one compound from thestabiliser group.

This invention also relates to an additive blend, which comprises (α) atleast one additive selected from the stabiliser, antistatic agent,nucleating agent, biocide and/or flame retardant group, and (β) at leastone polymeric dispersing or solvating agent having amphiphilicproperties.

Also preferred are additive blends wherein the weight ratio ofcomponents (α):(β) is from 100:0.01 to 0.01:100.

This invention also relates to a process for the improved dispersion ofadditives selected from the stabiliser, antistatic agent, nucleatingagent, biocide and/or flame retardant group in synthetic polymers, whichcomprises incorporating therein, or applying thereto, at least onepolymeric dispersing or solvating agent having amphiphilic properties.

This invention also relates to a process for stabilising syntheticpolymers against oxidative, thermal or light-induced degradation, whichcomprises incorporating therein, or applying thereto, at least onecomponent (b) and (c) each, with the proviso that component (b) containsat least one compound from the stabiliser group.

The components (b) and (c) preferably employed for the uses andprocesses disclosed above are the same as those described for thecompositions containing a synthetic polymer.

The following Examples illustrate the invention in more detail. Parts orpercentages are by weight.

EXAMPLE 1

Enhancing the effect of nucleating agents in polypropylene by means ofpolymeric dispersing or solvating agents having amphiphilic properties.

1.5 kg of polypropylene powder (Profax®6561, of Montell) are, mixed tohomogeneity in a high-speed mixer with 0.10% of Irgafos®168[tris(2,4-di-tert-butylphenyl)phosphite], 0.05% of Irganox®1010[pentaerythritol-tetrakis-[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate];0.10% of calcium stearate and with the additives listed in Table 1(nucleating agents and dispersing or solvating agents), and this blendis then extruded in a twin-screw extruder, of Berstorff, at atemperature of at most 250° C. After drawing the extrudate through awater-bath to cool, it is granulated. 80×90 mm and 2 mm thick testpanels are moulded from these granules by means of an injection mouldingmachine (Arburg 320 S) at a temperature of at most 250° C. E-modulus inmegapascal (Mpa), haze in percent and clarity of these test panels aremeasured in accordance with the Euro-norm (EN) ISO 527-1. The higher thevalues for the E-modulus and the clarity, the better the dispersion ofthe additives in polypropylene and the higher the transparency of thepolypropylene. The smaller the values for the haze, the better thedispersion of the additives in the polypropylene.

TABLE 1 E-modulus Haze Clarity Examples Additives (MPa) (%) (%) Example1a^(a)) 0.10% Irgaclear ® DM^(c)) 1517 70.6 82.5 Example 1b^(a)) 0.20%Wax P 121 ® ^(d)) 1550 89.2 12.0 Example 1c^(a)) 0.20% Tegomer ® DA100^(e)) 1520 87.8 12.0 Example 0.10% Irgaclear ® DM^(c)) 1552 57.5 89.41d^(b)) 0.20% Wax P 121 ® ^(d)) Example 1e^(b)) 0.10% Irgaclear ®DM^(c)) 0.20% Tegomer ® DA 100^(e)) 1571 53.7 89.6 Footnotes ^(a)) to^(e)) see end of Table 8 (Example 8).

EXAMPLE 2

Enhancing the long-term temperature stability of polypropylene by meansof polymeric dispersing or solvating agents having amphiphilicproperties.

1.5 kg of polypropylene powder (Profax®6501, of Montell) are mixed tohomogeneity in a high-speed mixer with 0.10% of Irgafos®168[tris(2,4-di-tert-butylphenyl)phosphite], 0.05% of Irganox®1010[pentaerythritol-tetrakis-[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate];0.10% of calcium stearate and with the additives listed in Table 2(dispersing or solvating agents), and this blend is then extruded in atwin-screw extruder, of Berstorff, at a temperature of at most 250° C.After drawing the extrudate through a waterbath to cool, it isgranulated. 80×90 mm and 2 mm thick test panels are then moulded fromthese granules by means of an injection moulding machine (Arburg 320 S)at a temperature of at most 250° C. One part of these panels is exposedto artificial ageing in a circulating air oven at 135° C. and the otherat 150° C. The time until these panels become brittle is measured indays. The more time this takes, the more effective the additives. Theresults are compiled in Table 2.

TABLE 2 Days until embrittlement Examples Additives at 135° C. at 150°C. Example 2a^(a)) —  45 14 Example 2b^(b)) 1.00% Wax P 121 ® ^(d)) >7031 Example 2c^(b)) 1.00% Tegomer ® DA 100^(e)) >70 27 Example 2d^(b))1.00% Tegomer ® DA 102^(f)) >70 31 Footnotes ^(a)), ^(b)), ^(d) e)) and^(f)) see end of Table 8 (Example 8).

EXAMPLE 3

Effect of polymeric dispersing or solvating agents having amphiphilicproperties on the long-term temperature stability of talcum-filledpolypropylene.

1.5 kg of polypropylene powder (Profax®6501, of Montell) are mixed tohomogeneity in a high-speed mixer with 0.10% of Irgafos®168[tris(2,4-di-tert-butylphenyl)phosphite], 0.05% of Irganox®1010[pentaerythritol-tetrakis-[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate];20% of talcum and 0.10% of calcium stearate and with the additiveslisted in Table 3 (dispersing or solvating agents), and this blend isthen extruded in a twin-screw extruder, of Berstorff, at a temperatureof at most 250° C. After drawing the extrudate through a water-bath tocool, it is granulated. 80×90 mm and 2 mm thick test panels are thenmoulded from these granules by means of an injection moulding machine(Arburg 320 S)- at a temperature of at most. 250° C. One part of thesepanels is exposed to artificial ageing in a circulating air oven at 135°C. and the other at 150° C. The time until these panels become brittleis measured in days. The more time it takes, the more effective theadditives. The results are compiled in Table 3.

TABLE 3 Days until embrittlement Examples Additives at 135° C. at 150°C. Example 3a^(a)) —  7  2 Example 3b^(b)) 3.0% Wax P 121 ® ^(d)) 52 20Example 3c^(b)) 3.0% Tegomer ® DA 102^(f)) 59 26 Footnotes ^(a)), ^(b)),^(d)) and ^(f)) see end of Table 8 (Example 8).

EXAMPLE 4

Effect of polymeric dispersing or solvating agents having amphiphilicproperties on the long-term temperature stability of polypropylene.

1.5 kg of polypropylene powder (PP Polychim®B10 FB, of Polychimie,France) are mixed to homogeneity in a high-speed mixer with 0.10%Irganox®HP 225 (Ciba Spezialitätenchemie AG, consisting of 42.5% ofIrgafos®168 [tris(2,4-di-tert-butylphenyl)phosphite], 42.5% ofIrganox®1010[pentaerythritol-tetrakis-[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]and 15% of HP-1360® [mixture of about 85 parts by weight of3-(3,4-dimethylphenyl)-5,7-di-tert-butylbenzofuran-2-one and about 15parts by weight of3-(2,3-dimethylphenyl)-5,7-di-tert-butylbenzofuran-2-one, structuralformulae see footnote g) at the end of Table 8]) and 0.05% of DHT 4A®(Kyowa Chemical Industry Co., Ltd. [Mg_(4.5)Al₂(OH)₁₃CO₃.3.5 H₂O]) andwith the additives listed in Table 4 (dispersing or solvating agents),and this blend is then extruded in a twin-screw extruder, of Berstorff,at a temperature of at most 250° C. After drawing the extrudate througha waterbath to cool, it is granulated. 80×90 mm and 2 mm thick testpanels are then moulded from these granules by means of an injectionmoulding machine (Arburg 320 S) at a temperature of at most 220° C. Thetest panels are stored in a conditioned room for 30 days at 50° C. andat 95% relative humidity. The Yellowness Index (YI) of these test panelsis determined in accordance with ASTM D 1925-70. Low YI values signifylittle discoloration, high YI values strong discoloration of thesamples. The less discoloration, the more effective the stabiliser orstabiliser blend. The results are compiled in Table 4.

TABLE 4 Yellowness Index before after storage Examples Additives storage(30 days/50° C.) Example 4a^(a)) — 3.01 4.48 Example 4b^(b)) 0.02%Tegomer ® DA 102^(f)) 0.42 1.89 Example 4c^(b)) 0.01% Tegomer ® DA102^(f)) 0.29 1.90 0.01% Irganox ® 1310^(h)) Footnotes ^(a)), ^(b)),^(f)) and ^(h)) see end of Table 8 (Example 8).

EXAMPLE 5

Effect of polymeric dispersing or solvating agents having amphiphilicproperties on the long-term temperature stability of polypropylene.

The results compiled in Table 5 are obtained in analogy to Example 4 byreplacing 0.05% of DHT 4A® (Kyowa Chemical Industry Co., Ltd.[Mg_(4.5)Al₂(OH)₁₃CO₃.3.5 H₂O]) with 0.10% of calcium stearate.

TABLE 5 Yellowness Index before after storage Examples Additives storage(30 days/50° C.) Example 5a^(a)) — −0.14 3.62 example 5b^(b)) 0.05%Tegomer ® DA 102^(f)) 0.07 1.72 Footnotes ^(a)), ^(b)) and ^(f)) see endof Table 8 (Example 8).

EXAMPLE 6

Effect of polymeric dispersing or solvating agents having amphiphilicproperties on the gloss of polypropylene filled with talcum and carbonblack.

1.5 kg of polypropylene powder (Daplen® KS 10, of Borealis, Linz,Austria, containing, 20% of talcum and 1% of carbon black) are mixed tohomogeneity in a high-speed mixer with 0.10% of trgafos®168[tris(2,4-di-tert-butylphenyl)phosphite], 0.05% of Irganox®1010[pentaerythritol-tetrakis-[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate];0.20% of Chimassorb®2020 [Ciba Speziealitätenchemie AG, structuralformula see footnote i) at the end of Table 8] and with the additiveslisted in Table 6 (dispersing or solvating agents), and this blend isthen extruded in a twin-screw extruder, of Berstorff, at a temperatureof at most 250° C. After drawing the extrudate through a waterbath tocool, it is granulated. 40×60 mm and 2 mm thick test panels are thenmoulded from these granules by means of an injection moulding machine(Arburg 320 S) at a temperature of at most 250° C. The panels areexposed to artificial weathering in an Atlas Weather-O-meter Ci 65A at ablack panel temperature of 63° C. without spraying with water. After 100hours each, samples are taken for surface measurements. The gloss of thesamples is determined in accordance with DIN 67530. The higher thevalues in percent, the more effective the additives. The results arecompiled in Table 6.

TABLE 6 Gloss after x hours artificial weathering in % ExamplesAdditives 0 h 1000 h 2000 h Example 6a^(a)) — 49 45 35 Example 6b^(b))0.10% Tegomer ® DA 102^(f)) 56 51 49 Footnotes ^(a)), ^(b)) and ^(f))see end of Table 8 (Example 8).

EXAMPLE 7 Enhancing the long-term temperature stability of polypropylenefilled with talcum and carbon black by means of polymeric dispersing orsolvating agents having amphiphilic properties.

1.5 kg of polypropylene powder (Daplen® KS 10, of Borealis, Linz,Austria, containing 20% of talcum and 1% of carbon black) are mixed tohomogeneity in a high-speed mixer with 0.10% of Irgafos®168[tris(2,4-di-tert-butylphenyl)phosphite], 0.05% of Irganox®1010[pentaerythritol-tetrakis-[3-(3,5-di-tert-butyl-4-hydroxypheny)propionate];0.10% of Irganox®PS 802 [thiodipropionic acid-di-stearyl ester], 0.20%of Chimassorb®2020 [Ciba Spezialitätenchemie AG, structural formula seefootnote i) at the end of Table 8] and with the additives listed inTable 7 (dispersing or solvating agents), and this blend is thenextruded in a twin-screw extruder, of Berstorff, at a temperature of atmost 250° C. After drawing the extrudate through a waterbath to cool, itis granulated. 80×90 mm and 2 mm thick test panels are then moulded fromthese granules by means of an injection moulding machine (Arburg 320 S)at a temperature of at most 250° C. These panels are exposed toartificial ageing in a circulating air oven at 150° C. The time untilthe panels become brittle is measured in days. The more time this takes,the more effective the additives. The results are listed in Table 7.

TABLE 7 Days until embrittlement at Examples Additives 150° C. Example7a^(a)) — 24 Example 7b^(b)) 0.10% Tegomer ® DA 102^(f)) 32 Footnotes^(a)), ^(b)) and ^(f)) see end of Table 8 (Example 8).

EXAMPLE 8

Effect of polymeric dispersing or solvating agents having amphiphilicproperties on the gloss of low-density linear polyethylene (LLDPE).

1.5 kg of LLDPE (LE 8001®, of Borealis, Linz, Austria) are mixed tohomogeneity with 0.05% of Irgafos®168[tris(2,4-di-tert-butylphenyl)phosphitel, 0.05% of Irganox®1010(pentaerythritol-tetrakis-[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate];and with the additives listed in Table 8 (dispersing or solvatingagents), and this blend is then extruded in a single-screw extruder, ofCollin (Germany), at a temperature of at most 230° C. After drawing theextrudate through a waterbath to cool, it is granulated. 40×60 mm and 2mm thick test panels are then moulded from these granules by means of aninjection moulding machine (Arburg 320 S) at a temperature of at most230° C. These panels are exposed to artificial weathering in an AtlasWeather-O-meter Ci 65A at a black panel temperature of 100° C. withoutspraying with water. The gloss of the-samples is determined after 38days in accordance with DIN 67530. The higher the values in percent, themore effective the additives. The results are compiled in Table 8.

TABLE 8 Gloss after 38 days of artificial Examples Additives weatheringin % Example 8a^(a)) — 20 Example 8b^(b)) 0.05% Tegomer ® DA 102^(f)) 58^(a))Comparison Example. ^(b))Example of this invention.^(c))Irgaclear ® DM (Ciba Spezialitätenchemie AG) is a nucleating agentand denotes (1.3:2.4)-diparamethyldibenzylidene sorbitol of formula Ia

^(d)) Wax P 121 ® (of Th. Goldschmidt AG, Germany) is a dispersant waxcontaining Tegomer ® DA 100^(e)). ^(e))Tegomer ® DA 100 (of Th.Goldschmidt AG, Germany) is an acrylate-based polymeric dispersing orsolvating agent. ^(f))Tegomer ® DA 102 (of Th. Goldschmidt AG, Germany)is an acrylate-based polymeric dispersing or solvating agent. ^(g))HP136 ® (Ciba Spezialitätenchemie AG) is a mixture of about 85 parts byweight of the compound of formula Va and about 15 parts by weight of thecompound of formula Vb.

^(h))Irganox ® 1310 (Ciba Spezialitätenchemie AG) is a compound offormula AO-1

^(i))Chimasssorb ® 2020 (Ciba Spezialitätenchemie AG) is a compound offormula H1

wherein n′ is a number from 2 to 14.

What is claimed is:
 1. A composition, which comprises a) a syntheticpolymer subject to oxidative, thermal or light-induced degradation, b)at least one additive selected from the stabiliser, antistatic agent,nucleating agent, biocide and/or flame retardant group, and c) at leastone polymeric dispersing or solvating agent based on polyacrylates,polysiloxanes, polyvinyl acetate or on block copolymers containing atleast one block based on acrylate, acrylic acid or methacrylate havingamphiphilic properties.
 2. A composition according to claim 1, whereincomponent (a) is a polyolefin or polystyrene.
 3. A composition accordingto claim 1, wherein component (a) is polyethylene or polypropylene.
 4. Acomposition according to claim 1, wherein component (b) IS a stabiliserand/or nucleating agent.
 5. A composition according to claim 4, whereinthe stabiliser is a phenolic antioxidant, aminic antioxidant, UVabsorber, light stabiliser, metal deactivator, phosphite, phosphonite,hydroxylamine, nitrone, thiosynergist, peroxide-scavenging compound, acompound of the benzofuran-2-one type and/or a PVC heat stabiliser.
 6. Acomposition according to claim 4, wherein the nucleating agent is acompound of formula I

wherein R₁, R₂, R₃ and R₄ are each independently of one another hydrogenor C₁-C₄alkyl.
 7. A composition according to claim 1, wherein component(c) is a dispearsing or solvating agent based on polyacrylates orpolysiloxanes containing long-chain side-groups.
 8. A compositionaccording to claim 1, wherein component (b) is present in an amount from0.01 to 10%, based on the weight of component (a).
 9. Acomposition-according to claim 1, wherein component (c) is present in anamount from 0.01 to 10%, based on the weight of component (a).
 10. Acomposition according to claim 1, wherein additional additives arepresent besides the components (a), (b) and (c).
 11. A compositionaccording to claim 10, wherein the additional additives are fillers. 12.A composition according to claim 11, wherein the filler is talcum,kaolin, mica or calcium carbonate.
 13. An additive blend, whichcomprises α) at least one additive selected from the stabiliser,antistatic agent, nucleating agent, biocide and/or flame retardantgroup, and β) at least one polymeric dispersing or solvating agenthaving amphiphilic properties.
 14. An additive blend according to claim13, wherein the weight ratio of the components (α):(β) is from 100:0.01to 0.01:100.
 15. A process for improving the dispersion of additivesselected from the stabiliser, antistatic agent, nucleating agent,biocide and/or flame retardant group in synthetic polymers, whichprocess comprises incorporating therein, or applying thereto, aneffective dispersing amount of at least one component (c) as defined inclaim
 1. 16. A process for stabilising synthetic polymers againstoxidative, thermal or light-induced degradation, which comprisesincorporating therein, or applying thereto, an effective stabilizingamount of at least one component (b) and an effective dispersing amountof at least one component (c), each as defined in claim 1, with theproviso that component (b) contains at least one compound from thestabiliser group.